Mixed esters of methylol phenols



Patented Dec. 29, 1942 c 2,306,932

UNITED STATES PATENT OFFICE MIXED ESTERS OF METHYLOL PHENOLS Herman A. Brnson, Philadelphia, Pa assilnor to The Resinous Products a Chemical Company Philadelphia, Pa.

No Drawing. Application May 9, 1940, Serial No. 334,170

12 Claims. (01. 260-469) This invention relates to mixed esters of chosen for the present invention are preferably methylol phenols in which the acyloxy radical atthose oi the lower monobasic aliphatic acids such tached directly to the aromatic nucleus and the as acetic, propionic, butyric, isobutyric, or croacyloxyradical attached to the methylene groups tonic anhydrides. However, any in onocarboxylic are derived from different carboxylic acids. It acid anhydride may be used since the principle also relates to a process for preparing these mixed involved is the same. The higher acid anhydrides esters. cause diiiflculty in purifying the product on-ac- In copending application Serial No. 240,009 count of the low volatility oi the free acid and filed November 12, 1938, which on October 22, acid amide which result from the reaction. 1940, issued as U. S. Patent No. 2,218,739, it is The mixed esters obtained according to this shown that tertiary aminomethyl phenols may be invention are useiul as plasticizers, high boiling esterifled by treating them with an acyl chloride solvents and as intermediates in the manufacwhich may be derived from any monoor polytureioi synthetic resins, drying oils, etc. as is carboxylic acid. shown in copending applications Ser. Nos.

In copending application Serial No. 272,804 334,169, 334,171, and 334,172, all filed May 9, 1940. filed May 10, 1939, it is shown that when a terti- The esters of the tertiary "aminomethyl pheary aminomethyl phenol is heated with the annols which serve as the starting material may hydride of a monobasic carboxylic acid the hybe prepared from any tertiary aminomethyl droxyl group of the phenol is esterifled and simulphenol obtained by condensing any mononydric taneously the tertiary amino group is replaced by or polyhydric monocyclic phenol or polycyclic the acyloxy radical of the acid anhydride. This phenol having a bridged or condensed ring sysmay be exemplified by the following reaction: tem with one or more mols each of formaldehyde 0H and a non-aromatic secondary amine. The

a number of mols of formaldehyde and secondary ommofl'hflwmcoho amine employed in this condensation will depend on the type oi product desired and the number oireactive positions in the particular phenol em- 0 C 0 CH; played,

CH QC0CH +OH CON(CH +CH CQ0H The process is carried out in general by heating a mixture 01! the ester of a tertiary aminomethyl phenol and the acid anhydride to 100-200 C. In the case of the anhydrides which boil with- I has now been found that the esters of the in this range it is most convenient to boil the mixtertiary aminomethyl phenols will react i a, simture under a reflux condenser until the reaction ilar manner with anhydrides of carboxylic acids is comp and t distill 0111; the c d amide thus making available a process whereby mixed formed urin he r tionesters can be prepared in which the acyloxy The following examples will illustrate the ingroups attached directly to the aromatic nucleus vention. v

are different from those attached to the methyl- 40 Example 1 ene groups The acyloxy gmup attached dlrect' 140 g. of benzoyl chloride was added gradually,

ly to.the aromatic nucleus may be derived from while stirring, to a solution of 5 g, of .1

.3117 Wlymrmxync acid the droxybenzyl-N-dimethylamine in 300cc. 0! drybenzene. The mixture was stirred for two and phatic, aromatic, arylaliphatic, cycloaliphatic or heterocyclic series and may be saturated or unsaturated. On the other hand, the acyloxy group :3; 22333:; $2 fig gg g fi 3 5 5532: which re tzrllaces 1tlhe amino group of the tertiary lution keeping the temgerature bglow C aminome' yl p enol ester, when the latter is treated. with an acid anhydride, must be derived durmg the neutrahzatlon' The benzene layer 20m i1; moggcai-iboxyliigs acid. tWhenflanhydrides X3: i g imw geg wit: water, dried, and o poycar xy c ac reac on c tertiary We Y W D 011 On a S em aminomethyl phenols or their esters, resinous bath- The residual Oil, consisting essentially of products are obtained as is disclosed in copendyl minomethyll-phenyl benzoate, w ing application Serial No. 312,338 filed January 4, then acetylated as followsz. v 1940. For practical purposes the anhydrides 188 g. of this ester was boiled for 5 hours reaction product was then distilled invacuo'. The desired product came over between l5d-l8d J1 mm, as a colorless oil. It boiled mostly at 160-165;" (Ill-2 mm. Analysis and saponification value agreed with the form CEQQCOCHS Example 2 155 g. of a-ethylhexoyl chloride was added gradually, while stirring, to a solution of 207 g. of 2-(dimethylaminomethyl) -d-tertiary butylphenol in 300 c. of dry benzene. The resulting ester amine hydrochloride solution was cooled to 5 C. and made slightly alkaline with sodium hydroxide solution at a temperature not exceeding C. The benzene layer was separated, washed, dried, and evaporated in vacuo to give a pale yellow liquid consisting essentially of Z-(dimethylaminomethyl) -4-ter. butyl-phenyla-ethyl hexoate.

270 g. of this ester was boiled under reflux with 100 g. of acetic anhydride (90%) for 5 hours. The product was then distilled in vacuo, the fraction boiling at 165-180 C./ 1-2 mm. being collected. It consisted essentially of the mixed ester having the formula $HaOCOCH:

.onacnmcmornaco0-00.11.

It is a colorless liquid.

Example 3 ahNOHz-O. O-ommcm).

A mixture of 230 g. of the above base and 135 g. of acetic anhydride was heated under reflux at Mil-150 C. for 5 hours. The product was then stripped of low boiling material by heating in vacuo (2 mm.) to 150 C. The residue was a pale yellow oil weighing 264 g. Its analysis indicated a 95% content of a product having the formula.

ocownmcoo omcoocm-O O-cmocoom Example 4 (a) A mixture consisting of 165 g. of 2-dimethyl aminomethyD-4-ter. butylphenyl oleate and 50 g. of acetic anhydride was heated for 5 asoaaea under reflux with 82 a. oiacetic anhydride. The hours at -150" C. under a reflux condenser.

The product was heated in vacuo to 1 .75 C. at 3 mm, to remove low boiling components. The residual product was an oil consisting essentially of Z-acetoxymethyl-d-ter. butylphenyl oleate;

OCOCnHia CHEiCO OCH (b) When heated with acetic anhydride in the same manner, 2-di1nethylaminomethyl) -4-ter. butylphenyl ester of linseed oil fatty acids prepared from 2-(dimethylaminomethyl) 4 ter. butylphenol and the mixed acid chlorides of linseed oil fatty acids) gave a dark oil consisting essentially of the mixed linoleic and linolenic acid esters of 2-acetoxymethyl-4-ter. butylphenol.

Example 5 To a solution of 263 g. of 2-(dimethylaminomethyl)-4-ter.octylphenol in 800 cc. of benzene there was added gradually '78 g. of acetyl chloride while stirring and cooling to 10 C. In a short time the mixture solidified to a crystalline paste of the acetic acid ester hydrochloride which was filtered off, dissolved in water, and neutralized at 5 C. with a 10% solution of sodium hydroxide. The acetic acid ester of the free base having the formula (CHS)ICCH2(OH3)ZC OCOCH;

separated as an oil boiling at l53-155 C./2 mm.

A mixture consisting of 30 g. of the above ester and 18 g. of crotonic anhydride was heated for 5 hours at-" C. The excess crotonic anlmdride and the crotonic dimethyl amide formed were then distilled off under reduced pressure. The residual product was an oil consisting essentially of the mixed ester having the formula (CHmC omwmnoQ-ococm I moooon==cn-om Example 6 A mixture 01 46.7 g. 01' l-(dimethylaminomethyl) -2-naphthyl stearate CHaNUJE):

O C OCnHu and 20 g. of butyric anhydride was heated for five hours at 150 C. Excess butyric anhydride I and the butyric dimethyl amide formed were dis-, tilled of! under reduced pressure. The residual product was an oil, consisting essentially of the mixed butyrate stearate of a-methylol-p-naphthol having the formula CHQOGO CHaCHaCH;

Example 7 A mixture consisting of 58.4 g. of di-(2-di-, methylaminomethylxenyl) -phthalate OCOCuHACOO I CHSCHICOOCHO Ocmccocmcn;

CnHs CsH: Example 8 One mol of adipyl chloride was added gradually to 2 mols of Z-(dimethylaminomethyl) -pcresol dissolved in benzene. then neutralized with 10% sodium hydroxide solution at 510 C. The resulting ester solution -was washed and dried and the benzene evaporated off. The ester obtained corresponding to the formula ocowrmiooo I l unmen-Q Ocamcm).

CH: CH:

was then boiled with 2.5 mols of acetic anhydride at 140-145 C. for 6 hours. After distilling ofi acetic dimethylamide and excess acetic anhydride in vacuo, an excellent yield of a pale yellow oil was obtained consisting essentially of the mixed adipate-acetate, having the formula ocowumcoo HI CHI In a. similar manner, the monocarboxylic or polycarboxylic acid esters of morpholinomethylphenols, piperindinomethyl. phenols,. or other tertiary aminomethyl phenols, cresols, xylenols, naphthols, hydroxydiphenyls, benzyl phenols,

The product was cyclohexyl phenols, and other hydroxyaromatic compounds may be condensed with monocarboxylic acid anhydrides to form mixed esters of methylol phenols.

I claim;

1. The process of preparing mixed esters of methylol phenols which comprises heating to re.- acting temperatures a mixture of an ester of a tertiary aminomethyl phenol and the anhydride of a monobasic carboxylic acid which is difierent from the acid corresponding to the acyl radical of the ester of the tertiary aminomethyl phenol.

2. The process of preparing mixed esters. of methylol phenols which comprises heating to reacting temperatures a mixture, of a dicarboxylic acid ester of a tertiary aminom'ethyl phenol and the anhydrlde of a monobasic carboxylic acid.

3. The process of preparing mixed esters of methylol phenols which comprises heating to reacting temperatures a mixture of an ester of a tertiary aminomethyl phenol and the anhydride of a monobasic lower aliphatic carboxylic acid which is difierent from the acid corresponding to the acyl radical of the ester of the tertiary aminoethyl phenol.

4. The process which comprises heating to reacting temperatures a mixture of di-(Z-dimethylaminomethyl-4-methy1phenyl) -adipate and acetic anhydride.

5. The process which comprises heating to reacting temperatures a mixture of di- (Z-dimethylaminomethylxenyl)-phtha1ate and acetic anhydride. Y

6. The process which comprises heating to reacting temperatures a mixture of di-(2-dimethylaminomethyl-4-ter.butyl-phenyl) -sebacate a n d acetic anhydride.

7. Mixed esters of methylol phenols in which the methylo1 group is esterified with a monocarboxylic acid and the phenolic hydroxyl group is esterfied with a polycarboxylic acid.

, 8. Mixed esters of methylol phenols in which the methylol group is esterfied with a monocarboxylic acid and the phenolic hydroxyl group is esterfled with a dibasic carboxylic acid.

9. Mixed esters of methylolphenols in which I the methylol group is esterified with a monocarboxylic lower aliphatic acid and the phenolic hydroxyl group is esterified with a polycarboxylic acid.

10. An ester having the formula 1 CHzCOOCHg-Q 042112000011 11. An ester having the formula 0 c 0 0.3.0 o o I I cmcoocmO O-cmococm CaH; I

Ca s 12. An ester having the formula ocownmooo I l crncoocm-O O-cmocoom CAHrQBI') m can HERMAN A. BRUSON. 

